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Acta Cryst. (2009). E65, m139    [ doi:10.1107/S1600536808043808 ]

Bis{benzyl N'-[(1H-indol-3-yl)methylene]dithiocarbazato-[kappa]2N',S}copper(II) N,N-dimethylformamide disolvate

H. Khaledi, H. Mohd Ali and S. W. Ng

Abstract top

In the structure of [Cu(C17H14N3S2)2]·2C3H7NO, the Cu atom (site symmetry \overline{1}) is N,S-chelated by the two deprotonated Schiff-base anions that define a distorted square-planar geometry. An N-H...O hydrogen bond links the mononuclear complex to the DMF solvent molecules.

Related literature top

For the Schiff base ligand, see: Khaledi et al. (2008b). For the isostructural nickel analog, see: Khaledi et al. (2008a).

Experimental top

Benzyl (1H-indol-2-ylmethylene)hydrazinecarbodithioate (Khaledi et al., 2008b) (1 mmol, 0.33 g) was dissolved in ethanol (30 ml). To the clear solution was added an ethanol solution (10 ml) containing 1 mmol (0.09 g) of copper chloride dihydrate. The mixture was heated for an hour. The product that separated was recrystallized from DMF.

Refinement top

The C-bound H atoms were placed at calculated positions (C–H 0.95–0.99 Å) and were treated as riding on their parent C atoms, with U(H) set to 1.2–1.5 times Ueq(C). The amino H-atom was located in a difference Fourier map, and was refined with a distance restraint of N–H 0.88±0.01 Å; its temperature factor was freely refined.

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: pubCIF (Westrip, 2009).

Figures top
[Figure 1] Fig. 1. Thermal ellipsoid plot (Barbour, 2001) of Cu(C17H14N3).2DMF at the 70% probability level. Hydrogen atoms are drawn as spheres of arbitrary radius.
Bis{benzyl N'-[(1H-indol-3-yl)methylene]dithiocarbazato- κ2N',S}copper(II) N,N-dimethylformamide disolvate top
Crystal data top
[Cu(C17H14N3S2)2]·2C3H7NOZ = 2
Mr = 858.60F(000) = 894
Monoclinic, P21/cDx = 1.425 Mg m−3
Hall symbol: -P 2ybcMo Kα radiation, λ = 0.71073 Å
a = 10.4461 (2) ŵ = 0.80 mm−1
b = 20.0882 (3) ÅT = 100 K
c = 10.8333 (2) ÅIrregular block, brown
β = 118.366 (1)°0.25 × 0.15 × 0.05 mm
V = 2000.34 (6) Å3
Data collection top
Bruker SMART APEX
diffractometer		4594 independent reflections
Radiation source: fine-focus sealed tube3837 reflections with I > 2σ(I)
graphiteRint = 0.035
ω scansθmax = 27.5°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −13→13
Tmin = 0.825, Tmax = 0.961k = −25→26
18600 measured reflectionsl = −14→14
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.031Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0382P)2 + 0.7321P]
where P = (Fo2 + 2Fc2)/3
4594 reflections(Δ/σ)max = 0.001
256 parametersΔρmax = 0.36 e Å−3
0 restraintsΔρmin = −0.36 e Å−3
Crystal data top
[Cu(C17H14N3S2)2]·2C3H7NOV = 2000.34 (6) Å3
Mr = 858.60Z = 2
Monoclinic, P21/cMo Kα radiation
a = 10.4461 (2) ŵ = 0.80 mm−1
b = 20.0882 (3) ÅT = 100 K
c = 10.8333 (2) Å0.25 × 0.15 × 0.05 mm
β = 118.366 (1)°
Data collection top
Bruker SMART APEX
diffractometer		4594 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		3837 reflections with I > 2σ(I)
Tmin = 0.825, Tmax = 0.961Rint = 0.035
18600 measured reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.031H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.081Δρmax = 0.36 e Å−3
S = 1.04Δρmin = −0.36 e Å−3
4594 reflectionsAbsolute structure: ?
256 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cu10.50000.50000.50000.01678 (8)
O10.8350 (2)0.56467 (8)−0.10421 (17)0.0526 (5)
S10.51561 (5)0.61250 (2)0.51610 (5)0.02414 (11)
S20.61468 (5)0.70543 (2)0.37409 (5)0.02345 (11)
N10.60380 (15)0.57545 (7)0.32793 (14)0.0191 (3)
N20.56823 (15)0.51211 (7)0.35752 (15)0.0193 (3)
N30.72111 (17)0.49444 (7)0.03797 (16)0.0234 (3)
H3N0.756 (3)0.5192 (11)−0.006 (2)0.040 (6)*
N40.91692 (17)0.57480 (8)−0.26314 (16)0.0267 (3)
C10.81749 (19)0.68443 (8)0.27140 (19)0.0223 (4)
C20.9316 (2)0.68264 (9)0.4074 (2)0.0282 (4)
H20.91490.69370.48380.034*
C31.0699 (2)0.66472 (10)0.4321 (2)0.0338 (4)
H31.14690.66280.52580.041*
C41.0974 (2)0.64964 (10)0.3226 (2)0.0340 (5)
H41.19260.63760.34060.041*
C50.9852 (2)0.65223 (10)0.1870 (2)0.0315 (4)
H51.00300.64230.11080.038*
C60.8463 (2)0.66931 (9)0.1618 (2)0.0261 (4)
H60.76950.67070.06800.031*
C70.6635 (2)0.70369 (9)0.23471 (19)0.0245 (4)
H7A0.59680.67240.16200.029*
H7B0.64460.74850.19150.029*
C80.58034 (17)0.62208 (8)0.39595 (17)0.0188 (3)
C90.58804 (18)0.46384 (8)0.28764 (18)0.0204 (3)
H90.56410.42090.30710.024*
C100.63940 (18)0.46470 (8)0.18750 (17)0.0201 (3)
C110.68033 (19)0.51762 (9)0.13067 (19)0.0229 (4)
H110.67960.56320.15380.027*
C120.65845 (18)0.40510 (8)0.12243 (17)0.0196 (3)
C130.63965 (19)0.33709 (9)0.13551 (18)0.0234 (4)
H130.60620.32160.19800.028*
C140.6707 (2)0.29284 (9)0.0556 (2)0.0276 (4)
H140.65950.24640.06450.033*
C150.7185 (2)0.31520 (9)−0.0383 (2)0.0285 (4)
H150.73800.2837−0.09260.034*
C160.73753 (19)0.38186 (9)−0.05314 (18)0.0250 (4)
H160.76900.3972−0.11730.030*
C170.70879 (18)0.42596 (9)0.02967 (18)0.0211 (3)
C180.8710 (3)0.54041 (11)−0.1878 (2)0.0395 (5)
H180.86520.4934−0.19890.047*
C190.9269 (2)0.64686 (9)−0.2527 (2)0.0294 (4)
H19A0.92230.6613−0.16850.044*
H19B0.84600.6666−0.33580.044*
H19C1.01930.6613−0.24670.044*
C200.9516 (2)0.54244 (10)−0.3636 (2)0.0314 (4)
H20A0.94410.4941−0.35730.047*
H20B1.05100.5541−0.34270.047*
H20C0.88320.5573−0.45870.047*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.01726 (15)0.01781 (15)0.01939 (15)0.00000 (11)0.01205 (12)0.00001 (11)
O10.0872 (13)0.0476 (10)0.0468 (9)−0.0192 (9)0.0511 (10)−0.0044 (7)
S10.0345 (3)0.0189 (2)0.0316 (2)−0.00003 (17)0.0260 (2)−0.00067 (17)
S20.0308 (2)0.0175 (2)0.0305 (2)0.00151 (17)0.0214 (2)0.00143 (17)
N10.0217 (7)0.0178 (7)0.0208 (7)−0.0002 (5)0.0126 (6)0.0020 (6)
N20.0222 (7)0.0179 (7)0.0214 (7)−0.0007 (5)0.0134 (6)0.0007 (5)
N30.0284 (8)0.0236 (8)0.0266 (8)0.0016 (6)0.0198 (7)0.0027 (6)
N40.0282 (8)0.0283 (8)0.0251 (8)−0.0006 (6)0.0138 (7)0.0045 (6)
C10.0268 (9)0.0148 (8)0.0302 (9)−0.0002 (7)0.0175 (8)0.0050 (7)
C20.0309 (10)0.0290 (10)0.0281 (9)−0.0024 (8)0.0168 (8)0.0022 (8)
C30.0247 (10)0.0349 (11)0.0346 (11)−0.0042 (8)0.0082 (9)0.0018 (9)
C40.0256 (10)0.0290 (10)0.0506 (13)−0.0022 (8)0.0207 (10)−0.0036 (9)
C50.0329 (11)0.0303 (10)0.0405 (11)−0.0016 (8)0.0249 (10)−0.0031 (8)
C60.0285 (9)0.0252 (9)0.0290 (9)−0.0006 (7)0.0172 (8)0.0027 (7)
C70.0291 (9)0.0236 (9)0.0274 (9)0.0054 (7)0.0187 (8)0.0081 (7)
C80.0158 (8)0.0215 (8)0.0196 (8)0.0016 (6)0.0090 (7)0.0025 (6)
C90.0223 (9)0.0182 (8)0.0240 (9)−0.0011 (6)0.0137 (7)−0.0003 (7)
C100.0214 (8)0.0197 (8)0.0212 (8)−0.0004 (6)0.0118 (7)−0.0010 (7)
C110.0262 (9)0.0219 (8)0.0272 (9)0.0022 (7)0.0182 (8)0.0003 (7)
C120.0178 (8)0.0226 (8)0.0197 (8)0.0000 (6)0.0100 (7)−0.0026 (7)
C130.0223 (9)0.0239 (9)0.0259 (9)−0.0034 (7)0.0129 (8)−0.0027 (7)
C140.0238 (9)0.0227 (9)0.0355 (10)−0.0022 (7)0.0135 (8)−0.0060 (8)
C150.0254 (9)0.0303 (10)0.0310 (10)0.0022 (8)0.0143 (8)−0.0098 (8)
C160.0223 (9)0.0340 (10)0.0220 (9)0.0023 (7)0.0131 (8)−0.0034 (7)
C170.0192 (8)0.0237 (9)0.0210 (8)0.0025 (7)0.0101 (7)−0.0001 (7)
C180.0543 (14)0.0337 (11)0.0362 (11)−0.0107 (10)0.0262 (11)0.0016 (9)
C190.0338 (11)0.0283 (10)0.0271 (10)−0.0031 (8)0.0154 (9)0.0030 (8)
C200.0308 (10)0.0354 (11)0.0312 (10)0.0037 (8)0.0173 (9)0.0028 (8)
Geometric parameters (Å, °) top
Cu1—N21.9987 (14)C5—H50.9500
Cu1—N2i1.9987 (14)C6—H60.9500
Cu1—S12.2666 (4)C7—H7A0.9900
Cu1—S1i2.2666 (4)C7—H7B0.9900
O1—C181.234 (3)C9—C101.421 (2)
S1—C81.7392 (17)C9—H90.9500
S2—C81.7519 (17)C10—C111.394 (2)
S2—C71.8092 (17)C10—C121.450 (2)
N1—C81.285 (2)C11—H110.9500
N1—N21.4048 (18)C12—C171.401 (2)
N2—C91.306 (2)C12—C131.397 (2)
N3—C111.347 (2)C13—C141.382 (2)
N3—C171.381 (2)C13—H130.9500
N3—H3N0.88 (2)C14—C151.403 (3)
N4—C181.321 (2)C14—H140.9500
N4—C191.452 (2)C15—C161.374 (3)
N4—C201.454 (2)C15—H150.9500
C1—C61.390 (2)C16—C171.391 (2)
C1—C21.387 (3)C16—H160.9500
C1—C71.512 (2)C18—H180.9500
C2—C31.386 (3)C19—H19A0.9800
C2—H20.9500C19—H19B0.9800
C3—C41.380 (3)C19—H19C0.9800
C3—H30.9500C20—H20A0.9800
C4—C51.378 (3)C20—H20B0.9800
C4—H40.9500C20—H20C0.9800
C5—C61.386 (3)
N2—Cu1—N2i180.000 (1)S1—C8—S2112.60 (9)
N2—Cu1—S184.21 (4)N2—C9—C10130.93 (16)
N2i—Cu1—S195.79 (4)N2—C9—H9114.5
N2—Cu1—S1i95.79 (4)C10—C9—H9114.5
N2i—Cu1—S1i84.21 (4)C11—C10—C9130.77 (16)
S1—Cu1—S1i180.0C11—C10—C12105.86 (15)
C8—S1—Cu195.28 (6)C9—C10—C12123.36 (15)
C8—S2—C7104.55 (8)N3—C11—C10109.74 (15)
C8—N1—N2112.72 (13)N3—C11—H11125.1
C9—N2—N1114.11 (14)C10—C11—H11125.1
C9—N2—Cu1124.77 (12)C17—C12—C13118.93 (15)
N1—N2—Cu1121.10 (10)C17—C12—C10106.66 (15)
C11—N3—C17109.91 (15)C13—C12—C10134.40 (16)
C11—N3—H3N124.5 (15)C14—C13—C12118.64 (16)
C17—N3—H3N125.5 (15)C14—C13—H13120.7
C18—N4—C19120.47 (17)C12—C13—H13120.7
C18—N4—C20121.44 (17)C13—C14—C15121.20 (17)
C19—N4—C20118.02 (15)C13—C14—H14119.4
C6—C1—C2118.43 (17)C15—C14—H14119.4
C6—C1—C7117.81 (16)C16—C15—C14121.23 (17)
C2—C1—C7123.75 (16)C16—C15—H15119.4
C3—C2—C1120.16 (18)C14—C15—H15119.4
C3—C2—H2119.9C15—C16—C17117.19 (17)
C1—C2—H2119.9C15—C16—H16121.4
C4—C3—C2120.95 (18)C17—C16—H16121.4
C4—C3—H3119.5N3—C17—C16129.38 (16)
C2—C3—H3119.5N3—C17—C12107.84 (14)
C3—C4—C5119.34 (18)C16—C17—C12122.79 (16)
C3—C4—H4120.3O1—C18—N4125.0 (2)
C5—C4—H4120.3O1—C18—H18117.5
C4—C5—C6119.94 (18)N4—C18—H18117.5
C4—C5—H5120.0N4—C19—H19A109.5
C6—C5—H5120.0N4—C19—H19B109.5
C5—C6—C1121.17 (18)H19A—C19—H19B109.5
C5—C6—H6119.4N4—C19—H19C109.5
C1—C6—H6119.4H19A—C19—H19C109.5
C1—C7—S2118.16 (12)H19B—C19—H19C109.5
C1—C7—H7A107.8N4—C20—H20A109.5
S2—C7—H7A107.8N4—C20—H20B109.5
C1—C7—H7B107.8H20A—C20—H20B109.5
S2—C7—H7B107.8N4—C20—H20C109.5
H7A—C7—H7B107.1H20A—C20—H20C109.5
N1—C8—S1126.61 (13)H20B—C20—H20C109.5
N1—C8—S2120.80 (13)
N2—Cu1—S1—C8−1.75 (7)Cu1—N2—C9—C10−177.95 (14)
N2i—Cu1—S1—C8178.25 (7)N2—C9—C10—C11−2.0 (3)
C8—N1—N2—C9178.63 (15)N2—C9—C10—C12178.22 (17)
C8—N1—N2—Cu1−3.25 (19)C17—N3—C11—C100.1 (2)
S1—Cu1—N2—C9−179.02 (14)C9—C10—C11—N3−179.57 (17)
S1i—Cu1—N2—C90.98 (14)C12—C10—C11—N30.2 (2)
S1—Cu1—N2—N13.07 (11)C11—C10—C12—C17−0.39 (19)
S1i—Cu1—N2—N1−176.93 (11)C9—C10—C12—C17179.40 (15)
C6—C1—C2—C3−1.4 (3)C11—C10—C12—C13178.57 (19)
C7—C1—C2—C3−179.70 (17)C9—C10—C12—C13−1.6 (3)
C1—C2—C3—C41.2 (3)C17—C12—C13—C14−0.4 (2)
C2—C3—C4—C5−0.3 (3)C10—C12—C13—C14−179.23 (18)
C3—C4—C5—C6−0.5 (3)C12—C13—C14—C15−0.8 (3)
C4—C5—C6—C10.4 (3)C13—C14—C15—C160.7 (3)
C2—C1—C6—C50.6 (3)C14—C15—C16—C170.6 (3)
C7—C1—C6—C5179.01 (16)C11—N3—C17—C16179.22 (18)
C6—C1—C7—S2166.51 (13)C11—N3—C17—C12−0.3 (2)
C2—C1—C7—S2−15.1 (2)C15—C16—C17—N3178.73 (17)
C8—S2—C7—C1−80.69 (15)C15—C16—C17—C12−1.8 (3)
N2—N1—C8—S11.3 (2)C13—C12—C17—N3−178.72 (15)
N2—N1—C8—S2−179.21 (11)C10—C12—C17—N30.43 (18)
Cu1—S1—C8—N10.81 (16)C13—C12—C17—C161.7 (3)
Cu1—S1—C8—S2−178.73 (8)C10—C12—C17—C16−179.15 (16)
C7—S2—C8—N15.62 (16)C19—N4—C18—O1−0.7 (3)
C7—S2—C8—S1−174.81 (9)C20—N4—C18—O1−177.5 (2)
N1—N2—C9—C100.1 (3)
Symmetry codes: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3N···O10.88 (2)1.87 (2)2.742 (2)175 (2)
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N3—H3N···O10.88 (2)1.87 (2)2.742 (2)175 (2)
Acknowledgements top

We thank the University of Malaya for funding this study (Science Fund grants 12–02-03–2031 and 12–02-03–2051).

references
References top

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191.

Bruker (2007). APEX2 and SAINT . Bruker AXS Inc., Madison, Wisconsin, USA.

Khaledi, H., Mohd Ali, H. & Ng, S. W. (2008a). Acta Cryst. E64, m1615.

Khaledi, H., Mohd Ali, H. & Ng, S. W. (2008b). Acta Cryst. E64, o2107.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Westrip, S. P. (2009). publCIF. In preparation.